Hydroxymethylated,fluoroacylated aminohydroxy aromatic compounds

ABSTRACT

PERFLUOROACYLKAMINOHYDROXY AROMATIC COMPOUNDS ARE PROVIDED WHICH ARE OUTSTANDING FOR PRODUCING OIL AND WATER REPELLENT EFFECTS ON TEXTILES AS WELL AS INCREASING THE RESISTANCE TO SOILING BY OILY PARTICULATE SOIL. THE AROMATIC NUCLEUS WHICH MAY CONTAIN 1,2 OR 3 RINGS MAY CONTAIN 1 OR 2 AMINO GROUPS, 1 OR 2 HYDROXY GROUPS AND UP TO 2 HYDROXY METHYL GROUPS. ONE OR 2 OF THE AMINO GROUPS ARE ACYLATED WITH A PERFLUORO ACYL GROUP CONTAINING FROM 3 TO 21 CARBON ATOMS IN WHICH AT LEAST 70% OF THE HYDROGENS HAVE BEEN REPLACED WITH FLUORINE. THE COMPOUNDS MAY ALSO CONTAIN ALKYL SUBSTITUENTS OF FROM 1 TO 5 CARBON ATOMS.

United States Patent 3,564,029 HYDROXYMETHYLATED, FLUOROACYLATEDAMINOHYDROXY AROMATIC COMPOUNDS Domenick Donald Gagliardi, EastGreenwich, R.I., as-

signor to Colgate-Palmolive Company, New York, N.Y., a corporation ofDelaware No Drawing. Filed Nov. 7, 1967, Ser. No. 681,084 Int. C].(1091: 7/00 U.S. Cl. 260-404 8 Claims ABSTRACT OF THE DISCLOSUREPerfluoroacylaminohydroxy aromatic compounds are provided which areoutstanding for producing oil and water repellent effects on textiles aswell as increasing the resistance to soiling by oily particulate soil.The aromatic nucleus which may contain 1, 2 or 3 rings may contain 1 or2 amino groups, 1 or 2 hydroxy groups and up to 2 hydroxy methyl groups.One or 2 of the amino groups are acylated with a perfluoro acyl groupcontaining from 3 to 21 carbon atoms in which at least 70% of thehydrogens have been replaced with fluorine. The compounds may alsocontain alkyl substituents of from 1 to 5 carbon atoms.

lysts and to solid substrates having attached thereto the polymersproduced by alkaline catalysis of a monomer of hydroxymethylatedfluoroacylated aminohydroxy aromatic compound.

While man has used woven textiles for raiment for more than two thousandyears, it was not until about one hundred years ago that he sought tomake woven textiles water repellent. The first and, in the light ofrecent knowledge of the basic principles of surface free energy, contactangle and spreading coefficient, unsophisticated water-proofing agentswere various mixtures compounded according to cookbook recipes which,when applied to woven textiles, coated the surface and filled theinterstices of the woven fabric with air-impervious and water-repellentmaterial. This served to provide rainwear such as the Macintosh and thesouwester but was not completely satisfactory for other uses.

In the period 1935 to 1940 in Germany especially at Chemische FabrickePferze with an empirical approach and without understanding the basicprinciples of water repellency, a series of wax emulsions was developedwhich, when padded onto textiles, produced a high contact angle of waterdrops on the surface of the textile and a high degree of showerresistance without changing the porosity or air permeability of thetextile material. The fabrics so treated were not wettable by water orby waterborne stains because of the change in free energy of the fibersurfaces and not because, as in prior art treatments of closing theinterstices of the fabric with deposits of treating material. By the useof the new wax emulsionmetallic salts compositions, it became possibleto produce fabrics which had the feel and appearance of conventionaluntreated fabrics but did not look like oil-cloths, or rubberized coatedfabrics. The primary practical limitation Patented Feb. 16, 1971 of suchcompositions was and still is the lack of durability to washing and drycleaning. Products of this type generally comprise a compositioncontaining (a) a parafiin wax or mixtures of vegetable wax esters suchas Carnauba, Candelilla, or Sugar Cane Wax; (b) an emulsifying agent,generally glue, gelatin, and rosin soaps; and (c) an aluminum orzirconium salt, usually the formate or acetate. The primary function ofthe salt is to insolubilize the glue and other emulsifiers after theemulsion is deposited on the fabric.

A large variety of such products are still used as lowcost, non-durablewater repellents for textiles. Since neither thermosetting nor fiberreaction occurs with such products, they all are non-durable to washingand dry cleaning. Other than water repellency for rainwear fabrics, suchproducts produce fabrics which have a fair degree of spot-and-stainresistance to water-borne stains.

The search for durable or permanent water-repellent finishing materialsespecially for cellulosic fibers was initiated because of thedeficiencies of the afore-discussed wax emulsions. The first majorimproved product was offered in England under the trade name of Velan.Velan was octadecyloxymethyl pyridinium chloride, a quaternary ammoniumcompound made by the chloromethylation of octadecanol followed byquaternization with pyridine and having a composition corresponding tothe formula:

H H 0:0 0 123E310 0 H2111:

\OC Cl'H E This structure, unlike other quaternary ammonium compounds,is unstable and under acid conditions reacts with surfaces containingactive hydrogen, e.g., the hydrogen of a hydroxyl group in cellulosefibers. If Z be the core of the cellulose fiber and OH be an hydroxylgroup in the surface thereof, then the reaction can be represented bythe formula:

011E350 ONHCHQIE C which is available commercially as Zelan and NoraneR. The advantage of the stearamide product is greater initial waterrepellency and greater durability to washing. Such products are leadersin rainwear fabric finishes.

In the search for other fiber reactive or durable water repellents,other classes of materials have now evolved as represented by siliconewater repellents, methylol stearamide compositions (Permel, Ahcovel NW),hydrophobic resins (Norane GG, Ranedare R, Argus DWR), octadecylketenedimer (Aquapel), and others.

While durable water-repellent finishes had been initially developed forouterwearand rainwear-type applications, in the period 1950 to 1956 suchproducts began to be used widely on mens suitings, dress goods, andupholstery materials. In this exploitation of these finishes emphasiswas placed not on water repellency but on resistance to spotting andstaining by water-borne stains. This use continues. It had been observedthat fabrics treated with such durable water repellents had a highdegree of resistance to soiling by water-borne soils and stains and wereeasier to launder. The principal limitation of such finishes was thatthey attracted rather than repelled oily soils and the fabrics were notrepellent to staining by oil materials such as oils, greases, gravy,mayonnaise, etc.

In the early part of the decade of 1950 to 1960 based on work done atthe Naval Research Laboratory by Fox and Zisman and work done by theKellogg division, later to become a part of the operations of MinnesotaMining and Manufacturing Company, the latter announced the utility ofcertain fluorocarbon based chemicals as finishes for various fibers. Foxand Zisman had demonstrated the physiochemical principle of lowfree-energy surfaces and the relation to non-wetting with water and oilof surfaces treated with chemicals containing perfiuoroalkyl groups.

The practical developments of Minnesota Mining and Manufacturing Companyresulted in the first product directed to textile finishing. This wasand still is the product known as FC-l49. FC-l49 is a classical Wernercomplex of a carboxylic acid made by reacting one mol of the carboxylicacid with 2 mols of basic chromic chloride to obtain a reaction producthaving a composition represented by the formula:

The compound is water soluble and cationic in nature. It shows strongadhesion to anionic substrates such cellulose and Fiberglas. It alsocomplexes with proteinaceous materials such as wool, silk, and leatherto yield both waterand oil-repellent surfaces.

A second general class of products developed by Minnesota Mining andManufacturnig Company (often referred to as 3M) comprise latices ofperfluorochemicals. For example, some of these are believed to have acomposition corresponding to the formulae:

These various products made available by 3M" produced a great practicalimprovement in fabric finishes. Although of some merit for plain waterrepellency for outerwear finishing, the two products offered a solutionto obtaining water and oil repellency and practical resistance tostaining. Because of its hydrolytic instability, the Werner complexproduct has been limited to wool, leather, and upholstery finishes. Theaciylate products have become prominent in finishing cotton, rayon, andsynthetic fibers.

Thus, while the progress in the art of imparting waterrepellency totextiles has been noteworthy, the soiling problem has not been solved.Recognizing the need for reproducible results, those concerned withresearch in this field have developed a test for water repellency, atest for oil repellency, a test for resistance to water-borne and oilborne stains and, for houshold furnishings, the most important: a testto evaluate particulate soil repellency.

WATER REPELLENCY Resistance to Wetting (Spray Test) AATCC Standard TestMethod 22-1952 This test method is applicable to any textile fabric. Itmeasures the resistance of fabrics to wetting by a water spray, and theresults depend primarily on the degree of hydrophobicity inherent in thefibers and yarns and subsequent treatments applied. Water is sprayedagainst the taut surface of a test specimen. Evaluation of the wettedpattern is readily brought about by comparing the wetted pattern withstandard wetting-pattern pictures:

Rating: Appearance of test specimen 100 No sticking or wetting of theupper surface.

90 Slight random sticking or wetting of the upper surface.

80 Wetting of the upper surface at the spray points.

70 Partial wetting of the whole of the upper surface.

Complete wetting of the whole of the upper surface.

0 Complete wetting of the Whole of the upper and the lower surfaces.

When measuring the spray rating, especially of finishes of the presentinvention, it is not unusual to encounter a test specimen withsufficient hydrophobic properties to confine the area of wetting and yetpermit wetting through. Thus, it becomes necessary to have a rating forthis condition. The following illustrates this modification of thestandard wetting evaluation:

A spray rating number of /0 is reported for a spray pattern comparableto the standard 70 rating but the undersurface is also wetted to someextent. The 70 of the numerator indicates equivalence with the standardtest pattern for a rating of 70. The zero in the denominator indicateswetting to the undersurface of the cloth at the Wet areas.

The test specimens having a minimum size of 7" x 7" are conditioned at70 F. and 65 percent relative humidity for a minimum of four hoursbefore testing. The test specimen, fastened securely and wrinkle free ina metal hoop having a diameter of 6 inches, is placed and centered 6inches under a standard spray nozzle at an angle of 45 degrees to thehorizontal. Two hundred and fifty milliliters of water at i2 F. ispoured into the funnel attached above the spray nozzle. The spray laststwenty-five to thirty seconds at the end of which time the hoop is takenby one edge and the opposite edge tapped smartly once against a solidobject with the wet side facing the solid; this procedure is repeatedwith the hoop reversed degrees.

OIL REPELLENCY TEST 3M Oil Repellency Test: "3M Textile Chemicals(Appendix A, Test Methods, page 1) The Minnesota Mining andManufacturing Company oil repellency test is based upon the differentpenetrating properties of the two hydrocarbon liquids, mineral oiltNujol") and n-heptane. The Nujol-heptane proportions for each ratingwere selected by 3M so as to give oily stain resistant somewhatcomparable to the waterborne stain resistance corresponding to each ofthe spray Percent y volume Percent heptare,

y volume Oil repellency rating 1 No hold out to Nujoli The standardoil-heptane mixtures are contained in small stoppered medicine dropperbottles. A drop of each mixture is placed on the fabric. The appearanceof the test oil is observed through the drop. Note is made Whetherwetting or penetration has occurred. The number corresponding to thatmixture containing the highest percentage of heptane which does notpenetrate nor wet the fabric after three minutes is considered the oilrepellency rating of the system.

The change in the optical refractivity of the drop is often anindication of wetting. In some cases wetting can be better determined byobserving the other side of the fabric. In some cases of zerooil/heptane rating, the symbol 0+ has been used to indicate a modicum ofresistance to wetting by oil.

STAIN REPELLENCY Staining Tests in Anti-soiling Evaluation of theResistance of Textile Fabrics to Waterand Oil-borne Stains The followingprocedures were established in the application of liquid stainingmaterials more nearly approaching the materials producing waterandoil-borne stains to which household furnishings receive in actual dailyuse.

(a) The fabrics are stretched lightly on 12" x 31" frames. All or partof the frame area is used depending upon the amount of fabric available.The frames are supported at both ends with the fabric about 8 inchesabove a horizontal black surface. The fabric touches nothing.

(b) Three inch medicine droppers are used to draw the stains from theircontainers. A one cubic centimeter calibration is established and ismarked on the exterior of each dropper. The stains are squeezedvertically downward from a height 2 inches above the cloth.

(0) After five minutes the unabsorbed stain is wiped off the fabric withtwo sweeps of Kleenex and the stains rated as follows:

Rating: Appearance No visible stain. 4 Slight stain. 3 Easily noticeablestain. 2 Considerable stain. l Very heavily stained.

(The spread or lack of spread is not necessarily reflected in theseratings.)

(d) Duplicate sets of stains are applied in separate areas so thatone-half of the fabric can be washed. In most instances, the washing iscarried out with 50 grams of FAB, in a cotton cycle, and a dummy load tototal 5 pounds in a Norge Home Automatic Washer.

The following two lists describe the numbering system and organizationof the stains on the fabric:

Water stains:

(1) Instant Tea 1 (2) Sheaffers 232 Blue-Black Skrip (3) A & P ConcordGrape Juice (4) Ann Page Salad Mustard (5) Bosco Chocolate Syrup 6 Oilstains:

(6) Wesson Oil (7) Gulf Supreme Motor Oil 20/20 (8) Oleomargarine (9) LaRosa Tomato Sauce (10) Jergens Lotion Eight cubic centimeters of drypowder per 200 cubic centimeters of Water applied at 160 F.

2 Melted and applied at 160 F.

(Those skilled in the art will recognize that, while these stains arenot scientifically compounded, they are stains to which householdfurnishings are exposed in the use attendant upon everyday life.)

(When reporting the relative resistance to staining and relative ease ofremoving stain in laundering, the values from water-borne stains andoil-borne stains are averaged and reported. In all cases the stains areallowed to dry on the fabrics for twenty-four hours before washing.)

Household furnishings is a term used herein to designate all articles inthe home of prince or pauper which are washed regularly at relativelyfrequent intervals or semi-occasionally at relatively irregularinfrequent intervals. Household furnishings include bed linen, i.e.,sheets, pillowcases, blankets, tablecloths, napkins, curtains,draperies, underthings, shirts, dresses, sox, handkerchiefs, blouses,skirts, slipcovers, and the like. It will be recognized that the termhousehold furnishings is inclusive but not exclusive.

As everyone will recognize while the aforedescribed controlled stainingtests are extremely useful for evaluating the effectiveness of varioustextile finishes, the incidence of staining a shirt front with salad oil(Wesson Oil) is only occasional whereas the staining of the collar andcuffs of a mans shirt with the finely divided soil of the environmentmixed with the oily exudations of the healthy human skin is amoment-to-moment occurrence. Hence, important as the aforedescribedtests are, a test to evaluate the resistance of a finish to the pick-upof such soil, hereinafter designated oily particulate soil, i.e., a testto evaluate the ability to shed oily particulate soil and the ease withwhich such oily particulate soil is removed by laundering undercontrolled conditions of soiling is of greater importance. Such acontrolled test providing reproducible results has been developed and isdesignated the GRC Dry Soil Test.

GRC DRY SOIL TEST Fifteen to twenty 6" x 8" numbered specimens (usuallyx 80 cotton), including at least one untreated control, are tumbled forthirty minutes with 10 percent Cyanamid Soil based on the weight of thefabric. The tumbling is carried out in a 5-liter capacity Five MinuteHome Cleaner at 44 r.p.m.; six No. 8 Neoprene rubber stoppers aredistributed among the speciments to increase the mechanical action. Atthe end of the tumbling, the specimens are removed and each shaken upand down separately fifteen times by hand to remove surface dirt.

The specimens are then cut in two, to produce two 4" x 6" pieces.One-half is washed with 50 grams of FAB in a cotton cycle with a S-pounddummy load, then hung to dry, and lightly ironed under a clean cottoncloth.

The degree of soil is determined with the Photovolt Reflectance Meter(Tri Blue Filter). Six readings per specimen are taken. The average ofthe six readings is reported.

CYANAMID SOIL The American Cyanamid Synthetic Soil described below isalso recommended by the Minnesota Mining and Manufacturing Company. Thedry ingredients are blended thoroughly, dried in a forced draftconvection oven for eight hours at 50 C., then milled twenty-five hourswith ceramic balls and stored in a polyethylene bag.

7 Material: Percent by weight Peat Moss 38 Cement 17 Kaolin Clay l7Silica200 mesh 17 Furance Black 1.75 Red Iron Oxide 0.50 Mineral Oil8.75

1 R. T. Vanderbilt Peerless.

2 Davidson Chemical Company.

Benny & Smith C0. Molacco.

* C. K. Williams C0.

It has been found that hydroxymethylated, fluoroacylated derivatives ofaminohydroxy aromatic compounds having at least two active nuclearhydrogens may be used to treat textiles, i.e., fibers, yarns, fabrics,and the like composed of cellulosic, including natural such as cottonand regenerated proteinaceous including natural such as wool andsynthetic fiber and particularly fibers having active hydrogen in thesurface. It is to be observed that the compounds of the presentinvention can also be used for coating materials which do not haveactive hydrogen in the surface such as the polyalkylenes, e.g.,polypropylene, and metals such as steel.

In general, the compounds of the present invention are prepared bymethods of classical chemistry. Thus, an aromatic compound having onebenzene ring or two or more fused rings is reacted in known manner toobtain the hydroxy compound. The latter is then reacted in known mannerto obtain the amino hydroxy compound. While the single ring compoundsare limited to a single amino and a single hydroxy group, i.e.,paraaminophenol having two active nuclear hydrogens, the aromaticcompounds having two or more fused rings can have one or a plurality ofhydroxy groups and one or a plurality of amino groups provided theresulting compound has two active nuclear hydrogens. Thus, for example,the dimethylol derivative of paraaminophenol is illustrative of thesingle ring compounds while aminoalphanaphthol or 4-aminonaphthol isillustrative of the multi-ring compounds which can be used as startingmaterials for the preparation of the mono-methylol or dimethylolcompounds of the present invention.

Illustrative of the preparation of a perfiuoroacyl derivative ofparaaminophenol having the generic formula:

where Q is an alkyl group having 3 to 21 carbon atoms in which at least70 percent of the 5 to 43 hydrogen atoms has been replaced with fluorineatoms and the terminal, i.e., omega carbon atom has at least two andpreferably three fluorine atoms.

Thus, 0.1 mol of the butyl ester of perfluorooctanoic acid C F3(C F2)C|O CHzCI-IzCzlk is mixed with 0.1 mol of p-aminophenol, NH C H OH, and225 parts by weight of methyl ethyl ketone. The reaction mixture washeated to reflux temperature (80 C.) for 3.5 hours to effectammonolysis. The reaction can be The reaction mixture was stripped atelevated temperature to remove all solvents, i.e., methylethylketone andbutyl alcohol. To 25 parts by weight of the stripped residue were added5.5 parts by weight of percent methanol solution of formaldehyde. The pHof the mixture was adjusted to 11.4 by the addition of caustic soda andthe reaction mixture heated two hours at reflux to effect methylolation.The methylolation of the perfluorooctoyl-paminophenol can be representedby the equation:

While the reaction represented by Equation 3 involves the reaction ofthe perfluoroacyl-p-aminophenol with formaldehyde in the molal ratio ofl to 2, those skilled in the art will understand that theperfluoroacyl-p-aminophenol can be reacted with formaldehyde in themolal ratio of l to 1. Accordingly, the methylol derivatives ofperfluoroacylaminohydroxy aromatic compounds having two active hydrogenshave the generic formula:

o R. (Qd), HN .R( 0H (CH OID where R is the nucleus of an aminohydroxyaromatic compound having a single ring, two fused rings, or three fusedrings, Q has the same significance as in Formula 1, R is hydrogen oralkyl having one to five carbon atoms, n is 1 or 2, m is one or two, tis one or two, s an integer 6, 8, or 10 minus (m+n+t), and x is the sameas t.

The novel perfiuoroacyl aminohydroxy monomethylol and dimethylolcompounds are not to be confused with prior disclosed compounds assimple methylol phenols. For example, in U.S. Pat. No. 2,468,530, theafter treatment of viscose rayon to reduce the swelling value andincreasing the water resistance and wet strength of viscose rayon withmonoand di-substituted derivatives of monoand di-substituted phenolssuch as paracresol monoand di-alcohols represented by the formula:

where R is H or CH OH. However, these resins do not confer surface wateror oil repellency to textile fibers.

The perfluoroacyl derivatives of aminohydroxy aromatic compounds are notto be confused with the perfluorinated cyclohexyl carboxylic acid andcyclohexyl acetic acid derivatives described in U.S. Pat. No. 2,593,737having the composition represented by the generic formula RZ where R isa saturated polycarbon fluorocarbon radical containing at least threecarbon atoms and Z is a monocarboxyl radical or a carboncontainingderivative radical hydrolyzable thereto such as C F COOH,undecafluorocyclohexyl carboxylic acid.

In U.S. Pat. No. 2,495,239 a method for treating cellulose is described.The patented method comprises condensing in alkaline mediumpara-tertiary-amyl phenol and formaldehyde in the molecular ratio of 1:2and reacting the condensation product with cellulosic materialcontaining free hydroxyl groups and subjecting the cellulosic reactionproducts to thermal treatment to form resiniform bridge linkages betweenthe cellulose chains.

A process of rendering textile fabrics, yarns, and fibers waterproofwithout materially altering the general appearance of the fabric isdescribed in U.S. Pat. No. 2,257,088. These results are produced by theuse of compounds having the general structure in which Ar represents anaromatic nucleus of the benzene or naphthalene series carrying anuclearly bound oxygen and at least one hydrocarbon substituent of thealiphatic or cycloaliphatic series which contains eight or more carbonatoms and which is bound to the aromatic nucleus directly or through anether, carbonyl, carboxyl, or carbamido linkage. The nuclearly boundoxygen may be part of hydroxyl group or a part of a side chain. A and 13represent members of the group consisting of open chain, lower aliphaticgroups when taken singly and when taken together divalent groups whichjointly with the nitrogen form a heterocycle.

'In direct contrast to the materials described in the foregoing U.S.patents, the compounds of the present invention are high melting pointwaxes which either react with active hydrogen in the substrate in thepresence of an acid catalyst such as oxalic, phosphoric, and zincnitrate, or form a coating on the substrate be it fibrous such ascotton, wool, nylon, polyethylene, wood, steel, aluminum, glass, orother ceramic having no active hydrogen when an alkaline catalyst suchas NaOH, borax, and potassium methoxide is used.

Thus, for example, the dimethylol perfluorooctanoylaminophenol, thepreparation of which has been described hercinbefore, can be suspendedin water containing an acid catalyst, a fibrous material immersed in thewater, the treated fibrous material squeezed to at least 80 percent Wetpick-up and the treated fibrous material heattreated at a temperature inthe range of 250 to 300 F. for a period of time inversely proportionalto the temperature and for example five to ten minutes at 300 F. (80percent wet pick-up is a term meaning that the fibrous material contains80 percent by weight based on the weight of the fibrous material of theaqueous suspension). Hence, when the suspension contains 1 percent byweight of the methylol derivative, the fibrous material contains 0.8percent of the methylol derivative. Similarly, the methylol derivativecan be dissolved in a suitable solvent, for example, xylene containingan acid catalyst, the fibrous material immersed in the solution of themethylol derivative, the fibrous material squeezed to the predeterminedwet pick-up in the fibrous material, the solvent removed and the treatedfibrous material heat treated as previously described.

On the other hand, any solid substrate with or without active hydrogencan be treated to provide the solid substrate with a coating of thepolymerized methylol derivative. Thus, an aqueous suspension or asolution in a suitable organic solvent such as xylene containing analkaline catalyst for example NaOCH ZnO, and triethanolamine can beapplied to the solid substrate in any suitable manner as by dipping,spraying, spreading, or other means, the excess, if any, removed, andthe treated solid substrate heat treated at elevated temperatures of atleast 250 F. but below the decomposition temperature of the substrate orthe methylol polymer for a period of time inversely proportional to thetemperature, for example, at 300 F. for five to ten minutes.

Indicative of the waterand the oil-repellency and the resistance tosoiling by oily particulate soil is the treatment of cotton with thebis-formaldehyde adduct to perfluorooctanoyl-p-aminophenol:

as HOHzG-(f (IJOH2OH ONHQ where M Q 18 a( 2)o Reflectance Oil repellencyBefore After Treatment applied obtained wash wash 3% product plus 0.5%Zn(NO3)2-6H2O 100 33 62 Accordingly, the present invention provides (1)novel monoand di-methylolamino hydroxy aromatic compounds, (2) fibrousor solid substrates having associated therewith polymerized monoanddi-methylol aminohydroxy aromatic compounds, and (3) perfluoroacylaminohydroxy aromatic compounds.

I claim:

1. A perfluoroacylaminohydroxy aromatic compound having a compositioncorresponding to the formula:

where R is an aromatic residue having at least two active hydrogens,selected from the group consisting of benzene and naphthalene nucleii; Ris hydrogen or alkyl having one to five carbon atoms; Q is an alkylgroup having three to twenty-one carbon atoms in which at least percentof the 5 to 81 hydrogen atoms has been replaced with fluorine atoms; nis 1 or 2; t is 1 to 2; x is the same as t; m is 0, 1 or 2; sis aninteger 6 or 8 minus m-l-n-l-t.

2. A compound as defined in claim 1 wherein m is 0.

3. A compound as defined in claim 1 wherein m is 1 or 2.

4. A compound as defined in claim 2 wherein Q is pentadecafluorooctyl.

5. A compound as defined in claim 3 wherein Q is pentadecafiuorooctyl.

6. A compound as defined in claim 4 wherein n, t, and x are 1; R ishydrogen and s=4.

7. A compound as defined in claim 5 wherein m, n, t and x are 1; R ishydrogen and s=3.

8. A compound as defined in claim 5 wherein m=2; n, t and x are 1; R ishydrogen and s=2.

References Cited UNITED STATES PATENTS 2,4685 30 4/ 1949 Weeldenburg 8-116.4 2,495,239 1/1950 Drisch et al 8ll5.6 2,567,011 9/1951 Diesslin etal 260465.7 2,654,722 10/1953 Young et al. 260404 2,730,500 1/ 1956Young et a1. 260404 2,799,692 7/1957 Croxall et a1. 260404 3,198,7548/1965 Ahlbrecht et a1. 8--116.2 3,253,006 5/ 1966 Davis 2604043,322,490 5/1967 Gagliardi 8-116.2 3,352,625 11/1967 Gagliardi 8-1l6.23,232,697 2/1966 Needleman 260404 3,244,734 4/ 1966 Sonntag 260404 LEWISGOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner U.S. Cl. X.R.

